CN116902970A - High-performance graphene heat conducting film and preparation method thereof - Google Patents
High-performance graphene heat conducting film and preparation method thereof Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention discloses a high-performance graphene heat-conducting film and a preparation method thereof. According to the invention, the graphene sheets provide a heat transfer space for phonons, and the catalyst is added to help the formation of graphite crystal structures, so that the crystal structures of the graphene are more compact and ordered, structural defects can be effectively repaired, graphitization can be realized at a lower temperature or graphitization degree can be improved at the same temperature; the pyridine is favorable for improving the graphitization degree of polyimide, reducing the graphite spacing, forming polyimide with a high-orientation structure, and being used as an additional carbon source to repair the defects in the graphene sheets, so that the heat dissipation performance of the prepared graphene is further improved.
Description
Technical Field
The invention relates to the field of heat conducting film materials, in particular to a high-performance graphene heat conducting film and a preparation method thereof.
Background
As microelectronic devices move toward miniaturization and high density integration, space limitations of small devices do not allow the use of large heat sinks, and thin, highly conductive and flexible heat sinks are therefore needed to effectively manage heat dissipation. Among the existing heat dissipating materials, an artificial graphite heat dissipating film has characteristics of high thermal conductivity, high electrical conductivity, low density, and the like, compared with metal materials such as copper, aluminum, and the like, and is considered as a promising heat dissipating material for various electronic devices. Currently, commercial artificial graphite heat dissipation films are mainly prepared by pyrolysis of aromatic Polyimide (PI) films. PI is an excellent polymer material with unique molecular structure, and can be used as an excellent carbon source for graphite heat dissipation films. However, there are three main problems associated with the preparation of artificial graphite heat sink films by pyrolysis of PI films: (1) the graphitization degree of the artificial graphite heat dissipation film is low, and the interlayer distance is large, which prevents the improvement of the heat conductivity of the artificial graphite heat dissipation film; (2) the graphitization process requires long-time heat treatment (carbonization and graphitization) at extremely high temperature (usually more than 3000 ℃), and has the defects of high energy consumption, low discontinuous production yield and the like due to two heating and cooling processes; (2) is not resistant to bending and has poor toughness. The PI film body features that the PI film has chemical bond breaking and regenerating at high temperature, and the departure of non-carbon atoms causes crystal defects on microstructure, so that the PI film has poor toughness and is not resistant to bending.
As a novel carbon nanomaterial, graphene has remarkable heat conduction properties. It is reported that the thermal conductivity of the single-layer graphene at the ambient temperature can reach 5300W/(m.K). Thanks to the development of batch preparation of graphene oxide powder by a chemical oxidation method, a flexible heat dissipation material called a graphene heat conduction film has appeared in recent years. The graphene oxide has rich oxygen-containing functional groups, can be self-assembled to form a macroscopic material, and can be converted into a graphene film with extremely high thermal conductivity through heat treatment.
Firstly, because graphene oxide powder is mainly prepared by a chemical oxidation method, a certain structural defect is caused by introducing a large amount of oxygen-containing functional groups, gaps are generated in the subsequent high-temperature treatment process, and serious phonon scattering occurs in the heat transfer process, so that the heat conductivity is attenuated. Secondly, because a large number of gaps can be formed in the stacking and assembling process of the graphene sheets, phonons are scattered at the boundary of the sheets, and the transverse size of the graphene sheets can also obviously influence the heat conductivity of the graphene film. Some researchers have prepared graphene films by using large-sized graphene oxide sheets, but the thermal conductivity of these graphene films is still lower than expected. These large-sized graphene oxide sheets are all obtained by centrifugation, face great difficulty in actual production and exhibit extremely low efficiency. Meanwhile, the large-size graphene oxide sheets are poor in water solubility, the interlayer stacking is disordered, ordered graphite crystal domains are difficult to obtain, and the heat conductivity of the large-size graphene oxide sheets is also influenced. Finally, the heat treatment reduction process often requires extremely high temperatures and long heat treatments, and is energy-consuming, low in intermittent production yield, and high in manufacturing cost.
Therefore, there is a need in the art for improvements that provide a more reliable solution.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-performance graphene heat conduction film and a preparation method thereof aiming at the defects in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of a high-performance graphene heat conduction film comprises the following steps:
step 1, adding graphene oxide and pyromellitic dianhydride into a polar solvent, and performing ultrasonic dispersion to obtain a mixture;
step 2, adding 4,4' -diphenylmethane diisocyanate, toluene diisocyanate, a catalyst and pyridine into the mixture obtained in the step 1 at room temperature under nitrogen atmosphere, and stirring to obtain mixed slurry;
step 3, coating the mixed slurry obtained in the step 2 on a substrate to form a wet film, drying, peeling, and discarding the substrate to obtain the graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 in an argon atmosphere for carbonization treatment, and heating for graphitization treatment to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 to obtain the high-performance graphene heat conduction film.
Preferably, the preparation method of the high-performance graphene heat conducting film comprises the following steps:
step 1, adding 1-10 parts by weight of graphene oxide and 0.5-2 parts by weight of pyromellitic dianhydride into 90-99 parts by weight of polar solvent, and performing ultrasonic dispersion for 10-60min to obtain a mixture;
step 2, adding 0.2-1.0 part by weight of 4,4' -diphenylmethane diisocyanate, 0.2-1.0 part by weight of toluene diisocyanate, 0.001-0.01 part by weight of catalyst and 0.01-0.1 part by weight of pyridine into the mixture obtained in the step 1 at room temperature under a nitrogen atmosphere, and continuously stirring for 1-4 hours to obtain mixed slurry;
step 3, coating the mixed slurry obtained in the step 2 on a substrate to form a wet film with the thickness of 2-6 mm, drying, peeling, and discarding the substrate to obtain a graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 to 800-1200 ℃ in an argon atmosphere for carbonization treatment, and heating to 2500-2800 ℃ for graphitization treatment to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 to obtain the high-performance graphene heat conduction film.
Preferably, the polar solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the catalyst is one or more of ferrosilicon, graphite phase carbon nitride, boron carbide and silicon carbide.
Preferably, the viscosity of the mixed slurry obtained in the step 2 is 20000 to 100000mpa.s.
Preferably, the drying temperature of the wet film in the step 3 is 60-90 ℃ and the time is 1-3 h.
Preferably, the temperature rising rate of the carbonization treatment in the step 4 is 1-5 ℃/min, and the carbonization treatment time is 0.5-2 h.
Preferably, the temperature rising rate of the graphitization treatment in the step 4 is 5-20 ℃/min, and the graphitization treatment time is 0.5-2 h.
Preferably, the temperature of the hot-pressing treatment in the step 5 is 100-300 ℃, the pressure is 5-30 MPa, and the time is 0.5-2 h.
The invention also provides a high-performance graphene heat conducting film, which is prepared by the method.
The beneficial effects of the invention are as follows:
the invention provides a high-performance graphene heat conduction film and a preparation method thereof, wherein polyimide molecules are used as bridges to connect adjacent graphene oxide sheets, and a catalyst is added to reduce the activation energy of conversion from amorphous carbon to crystalline carbon, so that the temperature required by graphitization can be reduced;
in the invention, a one-step polycondensation method is adopted to synthesize ternary polymerization polyimide from aromatic dianhydride and aromatic diisocyanate; the addition of pyridine is beneficial to improving the graphitization degree of polyimide, reducing the interlayer spacing of graphite, reducing the edge defect of polyimide and being beneficial to forming an interlayer structure with high orientation; finally, in the continuous carbonization and graphitization process, polyimide is converted into an ordered graphite structure, and gaps among graphene sheets are filled, so that the graphene sheets become larger gradually; the graphite crystal derived from polyimide not only provides a channel for phonon transmission between graphene sheets, so that phonon scattering at the crystal boundary of the graphene sheets is reduced, but also pyridine and polyimide can be used as additional carbon sources to repair defects in the graphene sheets, and the heat dissipation performance of the prepared graphene is further improved;
the catalyst added in the invention can melt carbon, and after the carbon melting degree of disordered arrangement reaches saturation, part of melted carbon tends to low-energy-level graphite crystal form and is deposited; the ferrosilicon, graphite phase carbon nitride, boron carbide, silicon carbide and other catalysts can reduce the activation energy of the conversion of amorphous carbon to crystalline carbon, thereby reducing the graphitization temperature; the addition of the catalyst is beneficial to the formation of a graphite crystal structure, so that the crystal structure of the graphene is more compact and ordered, structural defects can be effectively repaired, and the graphitization degree can be improved at a lower temperature or at the same temperature; in addition, the catalyst has similar catalysis and enhancement effects on carbonization-graphitization of polyimide, and can improve the graphitization degree of polyimide.
In the invention, due to the catalytic graphitization effect of the catalyst, graphitization can be realized at a lower temperature or the graphitization degree can be improved at the same temperature; compared with the prior art, the technology can reach higher graphitization degree at lower temperature, which greatly saves energy consumption; meanwhile, due to continuous carbonization and graphitization, two times of temperature rise and fall do not exist, continuous production can be realized, and the productivity can be improved.
Drawings
Fig. 1 is a surface SEM image (a) and corresponding EDS spectrum (B) of the high-performance graphene thermal conductive film prepared in example 1;
fig. 2 is a cross-sectional SEM image of the high-performance graphene heat-conducting film prepared in example 1;
fig. 3 is a raman spectrum of the high performance graphene thermal conductive film prepared in example 1.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The test methods used in the following examples are conventional methods unless otherwise specified. The material reagents and the like used in the following examples are commercially available unless otherwise specified. The following examples were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a high-performance graphene heat conduction film and a preparation method thereof, wherein the method comprises the following steps:
step 1, adding 1-10 parts by weight of graphene oxide and 0.5-2 parts by weight of pyromellitic dianhydride into 90-99 parts by weight of polar solvent, and performing ultrasonic dispersion for 10-60min to obtain a mixture;
step 2, adding 0.2-1.0 part by weight of 4,4' -diphenylmethane diisocyanate, 0.2-1.0 part by weight of toluene diisocyanate, 0.001-0.01 part by weight of catalyst and 0.01-0.1 part by weight of pyridine into the mixture obtained in the step 1 at room temperature under a nitrogen atmosphere, and continuously stirring for 1-4 hours to obtain mixed slurry;
step 3, coating the mixed slurry obtained in the step 2 on a substrate to form a wet film with the thickness of 2-6 mm, drying, peeling, and discarding the substrate to obtain a graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 to 800-1200 ℃ in an argon atmosphere for carbonization treatment, and heating to 2500-2800 ℃ for graphitization treatment to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 to obtain the high-performance graphene heat conduction film.
In preferred embodiments, the polar solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
In a preferred embodiment, the catalyst is one or more of ferrosilicon, graphite phase carbon nitride, boron carbide and silicon carbide.
In a preferred embodiment, the substrate is a 450 μm thick polypropylene cloth.
In a preferred embodiment, the temperature rising rate of the carbonization treatment in the step 4 is 1-5 ℃/min, and the carbonization treatment time is 0.5-2 h.
In a preferred embodiment, the temperature rising rate of the graphitization treatment in the step 4 is 5-20 ℃/min, and the graphitization treatment time is 0.5-2 h.
In a preferred embodiment, the temperature of the hot-pressing treatment in the step 5 is 100-300 ℃, the pressure is 5-30 MPa, and the time is 0.5-2 h.
In the invention, pyridine can help to improve the graphitization degree of polyimide, reduce the graphite spacing and form polyimide with a high orientation structure.
In the invention, polyimide molecules are used as bridges to connect adjacent graphene oxide sheets, and a catalyst is added to reduce the activation energy of conversion from amorphous carbon to crystalline carbon, so that the graphitization temperature can be reduced to prepare the graphene-based composite heat-conducting material.
In the invention, polyimide is converted into a compact and ordered graphite structure after high-temperature heat treatment, and gaps among graphene sheets are filled, so that the graphene sheets become larger gradually. The graphene sheets provide heat transfer space for phonons, and the polyimide-derived small-sheet-layer graphite structure plays a bonding role between graphene sheets and fills gaps between the graphene sheets, so that interface density between the graphene sheets is improved, phonon scattering at grain boundaries of the graphene sheets is reduced, and the thermal conductivity of the graphene is further improved. In addition, pyridine and polyimide can be used as additional carbon sources to repair defects in the graphene sheets, so that the heat dissipation performance of the graphene-based composite heat conduction film is further improved.
According to the invention, the activation energy of the conversion from amorphous carbon to crystalline carbon can be reduced by adding a small amount of catalyst, and the formation of graphite crystal structure is facilitated, so that the crystal structure of graphene is more compact and ordered, structural defects can be effectively repaired, and graphitization can be realized at a lower temperature or the graphitization degree can be improved at the same temperature.
In the invention, the iron atoms in the ferrosilicon catalyst can promote the carbonization of polyimide and improve the graphitization degree of a graphite structure derived from polyimide; boron atoms in the boron carbide catalyst can be connected with carbon atoms broken by rearrangement of a carbon skeleton in the carbonization process through gap diffusion, so that the interlayer spacing of a graphite structure derived from polyimide is reduced; the silicon carbide catalyst can be decomposed during high-temperature heat treatment to generate gaseous silicon and graphitizable carbon, so that the graphitization degree of a graphite structure derived from polyimide is improved; the boron nitride catalyst can reduce the graphitization temperature of polyimide and improve the graphitization degree of polyimide. The addition of a small amount of catalyst not only has the effect of catalyzing graphitization on graphene, but also has the promotion effect on carbonization and graphitization of polyimide.
The foregoing is a general inventive concept and the following detailed examples and comparative examples are provided on the basis thereof to further illustrate the invention.
The main raw material sources in the following examples are as follows:
example 1
The preparation method of the high-performance graphene heat conduction film comprises the following steps of:
step 1, adding 6 parts by weight of graphene oxide and 1 part by weight of pyromellitic dianhydride into 94 parts by weight of N, N-dimethylacetamide, and performing ultrasonic dispersion for 30min to obtain a uniformly dispersed mixture;
step 2, slowly adding 1 part by weight of 4,4' -diphenylmethane diisocyanate, 1 part by weight of toluene diisocyanate, 0.006 part by weight of a ferrosilicon catalyst and 0.06 part by weight of pyridine into the mixture obtained in the step 1 at room temperature under a nitrogen atmosphere, and continuously stirring for 2 hours to obtain a mixed slurry with the viscosity of 60000 mPa.s;
step 3, coating the mixed slurry obtained in the step 2 on a polypropylene cloth with the thickness of 450 mu m to form a wet film with the thickness of 4mm, drying at 70 ℃ for 1.5 hours, peeling, and discarding the base material to obtain a graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 to 1100 ℃ at a heating rate of 3 ℃/min under argon atmosphere for carbonization treatment for 1h, and heating to 2800 ℃ at a heating rate of 10 ℃/min for graphitization treatment for 1h to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 for 1h at the temperature of 250 ℃ and under the pressure of 25MPa to obtain the high-performance graphene heat conducting film.
Example 2
The preparation method of the high-performance graphene heat conduction film comprises the following steps of:
step 1, adding 6 parts by weight of graphene oxide and 1 part by weight of pyromellitic dianhydride into 94 parts by weight of N, N-dimethylacetamide, and performing ultrasonic dispersion for 30min to obtain a uniformly dispersed mixture;
step 2, slowly adding 1 part by weight of 4,4' -diphenylmethane diisocyanate, 1 part by weight of toluene diisocyanate, 0.006 part by weight of graphite-phase carbon nitride catalyst and 0.06 part by weight of pyridine into the mixture obtained in the step 1 at room temperature under nitrogen atmosphere, and continuously stirring for 2 hours to obtain mixed slurry with the viscosity of 60000 mPa.s;
step 3, coating the mixed slurry obtained in the step 2 on a polypropylene cloth with the thickness of 450 mu m to form a wet film with the thickness of 4mm, drying at 70 ℃ for 1.5 hours, peeling, and discarding the base material to obtain a graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 to 1100 ℃ at a heating rate of 3 ℃/min under argon atmosphere for carbonization treatment for 1h, and heating to 2800 ℃ at a heating rate of 10 ℃/min for graphitization treatment for 1h to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 for 1h at the temperature of 250 ℃ and under the pressure of 25MPa to obtain the high-performance graphene heat conducting film.
Example 3
The preparation method of the high-performance graphene heat conduction film comprises the following steps of:
step 1, adding 6 parts by weight of graphene oxide and 1 part by weight of pyromellitic dianhydride into 94 parts by weight of N, N-dimethylacetamide, and performing ultrasonic dispersion for 30min to obtain a uniformly dispersed mixture;
step 2, slowly adding 1 part by weight of 4,4' -diphenylmethane diisocyanate, 1 part by weight of toluene diisocyanate, 0.006 part by weight of boron carbide catalyst and 0.06 part by weight of pyridine into the mixture obtained in the step 1 at room temperature under nitrogen atmosphere, and continuously stirring for 2 hours to obtain mixed slurry with the viscosity of 60000 mPa.s;
step 3, coating the mixed slurry obtained in the step 2 on a polypropylene cloth with the thickness of 450 mu m to form a wet film with the thickness of 4mm, drying at 70 ℃ for 1.5 hours, peeling, and discarding the base material to obtain a graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 to 1100 ℃ at a heating rate of 3 ℃/min under argon atmosphere for carbonization treatment for 1h, and heating to 2800 ℃ at a heating rate of 10 ℃/min for graphitization treatment for 1h to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 for 1h at the temperature of 250 ℃ and under the pressure of 25MPa to obtain the high-performance graphene heat conducting film.
Example 4
The preparation method of the high-performance graphene heat conduction film comprises the following steps of:
step 1, adding 6 parts by weight of graphene oxide and 1 part by weight of pyromellitic dianhydride into 94 parts by weight of N, N-dimethylacetamide, and performing ultrasonic dispersion for 30min to obtain a uniformly dispersed mixture;
step 2, slowly adding 1 part by weight of 4,4' -diphenylmethane diisocyanate, 1 part by weight of toluene diisocyanate, 0.006 part by weight of silicon carbide catalyst and 0.06 part by weight of pyridine into the mixture obtained in the step 1 at room temperature under nitrogen atmosphere, and continuously stirring for 2 hours to obtain mixed slurry with the viscosity of 60000 mPa.s;
step 3, coating the mixed slurry obtained in the step 2 on a polypropylene cloth with the thickness of 450 mu m to form a wet film with the thickness of 4mm, drying at 70 ℃ for 1.5 hours, peeling, and discarding the base material to obtain a graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 to 1100 ℃ at a heating rate of 3 ℃/min under argon atmosphere for carbonization treatment for 1h, and heating to 2800 ℃ at a heating rate of 10 ℃/min for graphitization treatment for 1h to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 for 1h at the temperature of 250 ℃ and under the pressure of 25MPa to obtain the high-performance graphene heat conducting film.
Example 5
The preparation method of the high-performance graphene heat conduction film comprises the following steps of:
step 1, adding 6 parts by weight of graphene oxide and 1 part by weight of pyromellitic dianhydride into 94 parts by weight of N-methylpyrrolidone, and performing ultrasonic dispersion for 30min to obtain a uniformly dispersed mixture;
step 2, slowly adding 1 part by weight of 4,4' -diphenylmethane diisocyanate, 1 part by weight of toluene diisocyanate, 0.006 part by weight of a ferrosilicon catalyst and 0.06 part by weight of pyridine into the mixture obtained in the step 1 at room temperature under a nitrogen atmosphere, and continuously stirring for 2 hours to obtain a mixed slurry with the viscosity of 60000 mPa.s;
step 3, coating the mixed slurry obtained in the step 2 on a polypropylene cloth with the thickness of 450 mu m to form a wet film with the thickness of 4mm, drying at 70 ℃ for 1.5 hours, peeling, and discarding the base material to obtain a graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 to 1100 ℃ at a heating rate of 3 ℃/min under argon atmosphere for carbonization treatment for 1h, and heating to 2800 ℃ at a heating rate of 10 ℃/min for graphitization treatment for 1h to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 for 1h at the temperature of 250 ℃ and under the pressure of 25MPa to obtain the high-performance graphene heat conducting film.
Example 6
The preparation method of the high-performance graphene heat conduction film comprises the following steps of:
step 1, adding 8 parts by weight of graphene oxide and 1.5 parts by weight of pyromellitic dianhydride into 92 parts by weight of N, N-dimethylacetamide, and performing ultrasonic dispersion for 30min to obtain a uniformly dispersed mixture;
step 2, slowly adding 1.2 parts by weight of 4,4' -diphenylmethane diisocyanate, 1.2 parts by weight of toluene diisocyanate, 0.008 part by weight of a ferrosilicon catalyst and 0.08 part by weight of pyridine into the mixture obtained in the step 1 at room temperature under a nitrogen atmosphere, and continuously stirring for 2 hours to obtain mixed slurry with the viscosity of 80000 mPa.s;
step 3, coating the mixed slurry obtained in the step 2 on a polypropylene cloth with the thickness of 450 mu m to form a wet film with the thickness of 4mm, drying at 70 ℃ for 1.5 hours, peeling, and discarding the base material to obtain a graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 to 1100 ℃ at a heating rate of 3 ℃/min under argon atmosphere for carbonization treatment for 1h, and heating to 2800 ℃ at a heating rate of 10 ℃/min for graphitization treatment for 1h to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 for 1h at the temperature of 250 ℃ and under the pressure of 25MPa to obtain the high-performance graphene heat conducting film.
Example 7
The preparation method of the high-performance graphene heat conduction film comprises the following steps of:
step 1, adding 4 parts by weight of graphene oxide and 0.8 part by weight of pyromellitic dianhydride into 96 parts by weight of N, N-dimethylacetamide, and performing ultrasonic dispersion for 30min to obtain a uniformly dispersed mixture;
step 2, slowly adding 0.8 part by weight of 4,4' -diphenylmethane diisocyanate, 1.2 parts by weight of toluene diisocyanate, 0.004 parts by weight of a ferrosilicon catalyst and 0.05 part by weight of pyridine into the mixture obtained in the step 1 at room temperature under a nitrogen atmosphere, and continuously stirring for 2 hours to obtain mixed slurry with the viscosity of 40000 mPa.s;
step 3, coating the mixed slurry obtained in the step 2 on a polypropylene cloth with the thickness of 450 mu m to form a wet film with the thickness of 4mm, drying at 70 ℃ for 1.5 hours, peeling, and discarding the base material to obtain a graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 to 1100 ℃ at a heating rate of 3 ℃/min under argon atmosphere for carbonization treatment for 1h, and heating to 2800 ℃ at a heating rate of 10 ℃/min for graphitization treatment for 1h to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 for 1h at the temperature of 250 ℃ and under the pressure of 25MPa to obtain the high-performance graphene heat conducting film.
Example 8
The preparation method of the high-performance graphene heat conduction film comprises the following steps of:
step 1, adding 6 parts by weight of graphene oxide and 1 part by weight of pyromellitic dianhydride into 94 parts by weight of N, N-dimethylacetamide, and performing ultrasonic dispersion for 30min to obtain a uniformly dispersed mixture;
step 2, slowly adding 1 part by weight of 4,4' -diphenylmethane diisocyanate, 1 part by weight of toluene diisocyanate, 0.006 part by weight of a ferrosilicon catalyst and 0.06 part by weight of pyridine into the mixture obtained in the step 1 at room temperature under a nitrogen atmosphere, and continuously stirring for 2 hours to obtain a mixed slurry with the viscosity of 60000 mPa.s;
step 3, coating the mixed slurry obtained in the step 2 on a polypropylene cloth with the thickness of 450 mu m to form a wet film with the thickness of 4mm, drying at 70 ℃ for 1.5 hours, peeling, and discarding the base material to obtain a graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 to 1100 ℃ at a heating rate of 3 ℃/min under argon atmosphere for carbonization treatment for 1h, and heating to 2800 ℃ at a heating rate of 10 ℃/min for graphitization treatment for 1h to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 for 1h at the temperature of 250 ℃ and under the pressure of 25MPa to obtain the high-performance graphene heat conducting film.
Example 9
The preparation method of the high-performance graphene heat conduction film comprises the following steps of:
step 1, adding 6 parts by weight of graphene oxide and 1 part by weight of pyromellitic dianhydride into 94 parts by weight of N, N-dimethylacetamide, and performing ultrasonic dispersion for 30min to obtain a uniformly dispersed mixture;
step 2, slowly adding 1 part by weight of 4,4' -diphenylmethane diisocyanate, 1 part by weight of toluene diisocyanate, 0.006 part by weight of a ferrosilicon catalyst and 0.06 part by weight of pyridine into the mixture obtained in the step 1 at room temperature under a nitrogen atmosphere, and continuously stirring for 2 hours to obtain a mixed slurry with the viscosity of 60000 mPa.s;
step 3, coating the mixed slurry obtained in the step 2 on a polypropylene cloth with the thickness of 450 mu m to form a wet film with the thickness of 4mm, drying at 70 ℃ for 1.5 hours, peeling, and discarding the base material to obtain a graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 to 1100 ℃ at a heating rate of 5 ℃/min under argon atmosphere for carbonization treatment for 1h, and heating to 2800 ℃ at a heating rate of 20 ℃/min for graphitization treatment for 1h to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 for 1h at the temperature of 250 ℃ and under the pressure of 25MPa to obtain the high-performance graphene heat conducting film.
Example 10
The preparation method of the high-performance graphene heat conduction film comprises the following steps of:
step 1, adding 6 parts by weight of graphene oxide and 1 part by weight of pyromellitic dianhydride into 94 parts by weight of N, N-dimethylacetamide, and performing ultrasonic dispersion for 30min to obtain a uniformly dispersed mixture;
step 2, slowly adding 1 part by weight of 4,4' -diphenylmethane diisocyanate, 1 part by weight of toluene diisocyanate, 0.006 part by weight of a ferrosilicon catalyst and 0.06 part by weight of pyridine into the mixture obtained in the step 1 at room temperature under a nitrogen atmosphere, and continuously stirring for 2 hours to obtain a mixed slurry with the viscosity of 60000 mPa.s;
step 3, coating the mixed slurry obtained in the step 2 on a polypropylene cloth with the thickness of 450 mu m to form a wet film with the thickness of 4mm, drying at 70 ℃ for 1.5 hours, peeling, and discarding the base material to obtain a graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 to 1000 ℃ at a heating rate of 3 ℃/min under argon atmosphere for carbonization treatment for 1h, and heating to 2600 ℃ at a heating rate of 10 ℃/min for graphitization treatment for 1h to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 for 1h at the temperature of 250 ℃ and under the pressure of 25MPa to obtain the high-performance graphene heat conducting film.
Example 11
The preparation method of the high-performance graphene heat conduction film comprises the following steps of:
step 1, adding 6 parts by weight of graphene oxide and 1 part by weight of pyromellitic dianhydride into 94 parts by weight of N, N-dimethylacetamide, and performing ultrasonic dispersion for 30min to obtain a uniformly dispersed mixture;
step 2, slowly adding 1 part by weight of 4,4' -diphenylmethane diisocyanate, 1 part by weight of toluene diisocyanate, 0.006 part by weight of a ferrosilicon catalyst and 0.06 part by weight of pyridine into the mixture obtained in the step 1 at room temperature under a nitrogen atmosphere, and continuously stirring for 2 hours to obtain a mixed slurry with the viscosity of 60000 mPa.s;
step 3, coating the mixed slurry obtained in the step 2 on a polypropylene cloth with the thickness of 450 mu m to form a wet film with the thickness of 4mm, drying at 70 ℃ for 1.5 hours, peeling, and discarding the base material to obtain a graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 to 800 ℃ at a heating rate of 3 ℃/min under argon atmosphere for carbonization treatment for 1h, and heating to 2500 ℃ at a heating rate of 10 ℃/min for graphitization treatment for 1h to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 for 1h at the temperature of 250 ℃ and under the pressure of 25MPa to obtain the high-performance graphene heat conducting film.
Example 12
The preparation method of the high-performance graphene heat conduction film comprises the following steps of:
step 1, adding 6 parts by weight of graphene oxide and 1 part by weight of pyromellitic dianhydride into 94 parts by weight of N, N-dimethylacetamide, and performing ultrasonic dispersion for 30min to obtain a uniformly dispersed mixture;
step 2, slowly adding 1 part by weight of 4,4' -diphenylmethane diisocyanate, 1 part by weight of toluene diisocyanate, 0.006 part by weight of a ferrosilicon catalyst and 0.06 part by weight of pyridine into the mixture obtained in the step 1 at room temperature under a nitrogen atmosphere, and continuously stirring for 2 hours to obtain a mixed slurry with the viscosity of 60000 mPa.s;
step 3, coating the mixed slurry obtained in the step 2 on a polypropylene cloth with the thickness of 450 mu m to form a wet film with the thickness of 5mm, drying at 70 ℃ for 1.5 hours, peeling, and discarding the base material to obtain a graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 to 1100 ℃ at a heating rate of 3 ℃/min under argon atmosphere for carbonization treatment for 1h, and heating to 2800 ℃ at a heating rate of 10 ℃/min for graphitization treatment for 1h to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 for 1h at the temperature of 250 ℃ and under the pressure of 25MPa to obtain the high-performance graphene heat conducting film.
Comparative example 1
The preparation method of the high-performance graphene heat conduction film provided by the embodiment is basically the same as that of the embodiment 1, and the difference is that: no catalyst is added in step 2.
Comparative example 2
The preparation method of the high-performance graphene heat conduction film provided by the embodiment is basically the same as that of the embodiment 1, and the difference is that: in the step 1, pyromellitic dianhydride is not added, and in the middle of the step 2, 4' -diphenylmethane diisocyanate and toluene diisocyanate are added.
Comparative example 3
The preparation method of the high-performance graphene heat conduction film provided by the embodiment is basically the same as that of the embodiment 1, and the difference is that: no catalyst was added in step 2 and the graphitization treatment temperature in step 5 was 3100 ℃.
Comparative example 4
The preparation method of the high-performance graphene heat conduction film provided by the embodiment is basically the same as that of the embodiment 1, and the difference is that: no pyridine was added in step 2.
Performance characterization and testing
1. Taking the high-performance graphene heat conduction film prepared in example 1 as an example, the following performance characterization is performed on the high-performance graphene heat conduction film:
referring to fig. 1, the surface SEM image (a) and the corresponding EDS energy spectrum (B) of the high-performance graphene heat-conducting film are obtained, and the high-performance graphene heat-conducting film is subjected to high-temperature reduction heat treatment and hot pressing, and the surface of the high-performance graphene heat-conducting film is flat, and only consists of carbon elements according to EDS energy spectrum analysis.
Referring to fig. 2, which is a cross-sectional SEM image of a high-performance graphene heat-conducting film, fig. 2 is a schematic drawing of a high-performance graphene heat-conducting film with different scale-up, and it can be seen that the high-performance graphene heat-conducting film is formed by stacking multiple layers of graphene in a compact and orderly manner.
Referring to fig. 3, a raman spectrum of the high performance graphene thermal conductive film, I D /I G =0.09 indicates that the high-performance graphene heat-conducting film has higher graphitization degree, I D /I G The ratio of the raman intensities of the D peak and the G peak; 2D Peak (2741 cm) -1 ) Is consistent with the raman characteristics of the multilayer graphene stack.
2. The high performance graphene heat conducting films prepared in examples 1-12 and comparative examples 1-3 were subjected to the following performance tests:
1. thickness test: the thickness of the high-performance graphene heat conducting film is tested according to the test method of the thickness of the ASTM D374M-2013 solid electrical insulating material;
2. density testing: testing the high-performance graphene heat conducting film by using a test method for measuring the density and specific gravity (relative density) of plastics by using a replacement method according to ASTM D792-2013;
3. thermal diffusivity test: testing the thermal diffusivity of the high-performance graphene heat conducting film by using a test method for measuring the solid thermal diffusivity by using a flash method according to ASTM E1461-2013;
4. thermal conductivity testing: calculating the thermal conductivity of the high-performance graphene heat conducting film according to the relationship between the thermal conductivity and the thermal diffusivity (thermal conductivity=thermal diffusivity×density×specific heat capacity);
the specific heat capacity is obtained by testing the specific heat capacity of the high-performance graphene heat conducting film according to an ASTM E1269-2011 test method for measuring special capacity by using a differential scanning calorimetry method, and then substituting the specific heat capacity into the relational expression, and calculating to obtain the heat conductivity.
The test results are shown in table 1 below:
TABLE 1
From the test results in table 1, the high-performance graphene heat conducting films prepared in examples 1 to 12 all have higher thermal diffusivity and thermal conductivity, which indicates that the high-performance graphene heat conducting films have excellent heat dissipation performance.
Compared with comparative example 1, examples 1-4 have higher thermal diffusivity and thermal conductivity, which shows that the catalyst plays an important role in greatly improving the heat dissipation performance of the high-performance graphene heat conducting film, and can effectively catalyze graphitization and improve graphitization degree at the same temperature.
Compared with comparative example 2, example 1 has higher thermal diffusivity and thermal conductivity, which indicates that polyimide molecules connected with graphene sheets as bridges play an important role in improving the heat dissipation performance of the high-performance graphene heat conducting film.
Compared with comparative example 3, the heat treatment in the presence of the catalyst in example 1 at a lower temperature instead achieves a higher thermal conductivity, which means that the addition of the active catalyst can reduce the activation energy of the conversion of amorphous carbon to crystalline carbon, thereby reducing the graphitization temperature, protecting the manufacturing equipment to a great extent and reducing the energy consumption.
Compared with comparative example 4, example 1 has higher thermal diffusivity and thermal conductivity, which indicates that pyridine plays a role in improving the heat dissipation performance of the high-performance graphene heat conduction film, can improve the graphitization degree of polyimide and serve as an additional carbon source to repair defects in graphene sheets, and further improves the heat dissipation performance of graphene.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (10)
1. The preparation method of the high-performance graphene heat conduction film is characterized by comprising the following steps of:
step 1, adding graphene oxide and pyromellitic dianhydride into a polar solvent, and performing ultrasonic dispersion to obtain a mixture;
step 2, adding 4,4' -diphenylmethane diisocyanate, toluene diisocyanate, a catalyst and pyridine into the mixture obtained in the step 1 at room temperature under nitrogen atmosphere, and stirring to obtain mixed slurry;
step 3, coating the mixed slurry obtained in the step 2 on a substrate to form a wet film, drying, peeling, and discarding the substrate to obtain the graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 in an argon atmosphere for carbonization treatment, and heating for graphitization treatment to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 to obtain the high-performance graphene heat conduction film.
2. The method for preparing the high-performance graphene heat conducting film according to claim 1, comprising the following steps:
step 1, adding 1-10 parts by weight of graphene oxide and 0.5-2 parts by weight of pyromellitic dianhydride into 90-99 parts by weight of polar solvent, and performing ultrasonic dispersion for 10-60min to obtain a mixture;
step 2, adding 0.2-1.0 part by weight of 4,4' -diphenylmethane diisocyanate, 0.2-1.0 part by weight of toluene diisocyanate, 0.001-0.01 part by weight of catalyst and 0.01-0.1 part by weight of pyridine into the mixture obtained in the step 1 at room temperature under a nitrogen atmosphere, and continuously stirring for 1-4 hours to obtain mixed slurry;
step 3, coating the mixed slurry obtained in the step 2 on a substrate to form a wet film with the thickness of 2-6 mm, drying, peeling, and discarding the substrate to obtain a graphene oxide-polyimide composite film;
step 4, heating the graphene oxide-polyimide composite film obtained in the step 3 to 800-1200 ℃ in an argon atmosphere for carbonization treatment, and heating to 2500-2800 ℃ for graphitization treatment to obtain a graphene-based composite foam film;
and 5, carrying out hot pressing treatment on the graphene-based composite foam film obtained in the step 4 to obtain the high-performance graphene heat conduction film.
3. The method for preparing a high-performance graphene heat-conducting film according to claim 2, wherein the polar solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
4. The method for preparing a high-performance graphene heat-conducting film according to claim 2, wherein the catalyst is one or more of ferrosilicon, graphite-phase carbon nitride, boron carbide and silicon carbide.
5. The method for preparing the high-performance graphene heat conducting film according to claim 2, wherein the viscosity of the mixed slurry obtained in the step 2 is 20000-100000 mpa.s.
6. The method for preparing the high-performance graphene heat-conducting film according to claim 2, wherein the drying temperature of the wet film in the step 3 is 60-90 ℃ and the time is 1-3 h.
7. The method for preparing the high-performance graphene heat-conducting film according to claim 2, wherein the heating rate of the carbonization treatment in the step 4 is 1-5 ℃/min, and the carbonization treatment time is 0.5-2 h.
8. The method for preparing the high-performance graphene heat-conducting film according to claim 2, wherein the temperature rising rate of the graphitization treatment in the step 4 is 5-20 ℃/min, and the graphitization treatment time is 0.5-2 h.
9. The method for preparing the high-performance graphene heat conducting film according to claim 2, wherein the temperature of the hot pressing treatment in the step 5 is 100-300 ℃, the pressure is 5-30 MPa, and the time is 0.5-2 h.
10. A high performance graphene thermal conductive film prepared by the method of any one of claims 1-9.
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